TWI519575B - A method for producing a polyvinyl alcohol film and a polyvinyl alcohol film, and a method for producing the same, - Google Patents

Description

Method for producing polyvinyl alcohol film and polyvinyl alcohol film, and laminate for heat transfer using the same

The present invention relates to a polyvinyl alcohol-based film excellent in mold release property, and more particularly to a release film-containing polyvinyl alcohol-based film which can be preferably used as a base film of a laminate for heat transfer and A method for producing a polyvinyl alcohol-based film, and a laminate for heat transfer using the polyvinyl alcohol-based film.

A method of adding a molded article includes a method of transferring a transfer layer of a film for transfer using a film for transfer. The film for transfer is a layer in which a transfer layer is laminated on the base film, and the transfer layer also includes a resin layer which serves as a protective layer for protecting the surface of the transferred material after transfer, and a pattern layer, an adhesive layer, and the like which are further included on the resin layer. By.

The transfer method is roughly classified into a hydraulic transfer method and a heat transfer method.

The hydraulic transfer method is a method in which a transfer layer such as a molded article is mortgaged on a transfer layer by superimposing a surface on the transfer layer side of the film for hydraulic transfer on the surface of the transfer layer and floating on the water surface. After transferring to the object to be transferred, the object to be transferred is taken out, washed with water, and the base film is dissolved and removed, whereby the pattern or the like is transferred to the object to be transferred. In such a hydraulic transfer method, a method of using a polyvinyl alcohol-based film excellent in water solubility as a base film is known (for example, Patent Documents 1 and 2).

On the other hand, the film for thermal transfer used in the heat transfer method is a film for thermal transfer in which a transfer layer is laminated in a peelable state on a base film made of a thermoplastic resin film or the like, and a resin layer which is a protective layer is usually used. It is composed of a resin composition excellent in surface physical properties such as hardness and solvent resistance. Use has The heat transfer method of the transfer film having such a configuration is a method in which the transfer layer is transferred to the surface by peeling off the base film from the transfer layer by pressure-bonding the surface on the transfer layer side of the transfer film to the surface of the transfer target. Transfer the surface of the object.

In the base film of the film for thermal transfer, a polyester resin film such as a polyethylene terephthalate film has been used in the past, but the polyester resin film usually has high affinity with the transfer layer, so that the melamine resin is used. A release agent layer such as a polysiloxane or a fluorine is interposed between the transfer layer and the base film to ensure mold release property. However, such a release agent treatment is disadvantageous in terms of environment and cost, and therefore a base film which does not require a release agent treatment is sought.

In this case, in recent years, a method of using a polyvinyl alcohol-based film in a base film of a laminate for heat transfer has been studied. For example, in Patent Document 3, a decorative film (heat transfer film) provided with a decorative layer (corresponding to a transfer layer) on one surface of a transparent film (corresponding to a base film) is disclosed as a polyvinyl alcohol as a transparent film. A resin film. Further, in Patent Document 4, a transfer film having a release layer, a pattern layer, and an adhesive layer on a single side of a base film is used, and a resin film containing a polyvinyl alcohol resin as a main component is used as the substrate. membrane.

Patent Document 1: Japanese Laid-Open Patent Publication No. 2007-152622

Patent Document 2: Japanese Laid-Open Patent Publication No. 2011-11540

Patent Document 3: Japanese Patent Laid-Open No. Hei 7-40515

Patent Document 4: Japanese Laid-Open Patent Publication No. Hei 9-277458

The polyvinyl alcohol-based film is known as a film having excellent mold release property, but is used as a base film of a laminate film for heat transfer without using a release agent. At the time, I sought to be much more releasable than before. In actuality, the commercially available polyvinyl alcohol-based film does not have such high mold release property, and even if the base film of the film for hydraulic transfer is transferred to the base film of the film for heat transfer, the mold release property cannot be satisfied.

Further, there is a demand for application of a release film in recent years or improvement of productivity of a decorative article in thermal transfer printing, and excellent mold release property is also required from the viewpoint of high-precision design formation. The polyvinyl alcohol-based film specifically used in the above patent documents is not sufficient.

The object of the present invention is to provide a polyvinyl alcohol-based film having excellent releasability, and in particular to provide a base film which can be preferably used for a laminate for heat transfer. The method for producing a polyvinyl alcohol-based film, a method for producing the polyvinyl alcohol-based film, and a laminate for transfer using the polyvinyl alcohol-based film, and the laminate system for heat transfer is used in a decoration method using a heat transfer method use.

The polyvinyl alcohol-based film of the present invention contains 1 to 20 parts by weight of a nonionic surfactant (B) containing an oxyethylene group and an oxypropylene group, based on 100 parts by weight of the polyvinyl alcohol-based resin (A). .

Previously, it has been known that a polyvinyl alcohol-based film usually contains a surfactant. At the manufacturing site of the polyvinyl alcohol-based film, it is ensured that the film-formed polyvinyl alcohol-based film is wound up on the drum or tape of the substrate at the time of film formation, and the ease of peeling from the substrate is prevented, thereby preventing the film from being taken up. From the viewpoint of adhesion at the time of extraction of the film at the time of extraction of the film, a surfactant is added in order to reduce adhesion. For example, in the above Patent Documents 1 and 2, polyoxyethylene sorbitan monolaurate or polyoxyethylene alkylamine can be used as the surfactant.

However, the "release property required for the base film of the film for thermal transfer" which is desired in the present invention is "the extent to which the temporarily formed layer of the laminated body can be easily peeled off without the release agent". The release property is much higher than the release property required at the manufacturing site of the polyvinyl alcohol film. Therefore, the content of the commonly used surfactant (a nonionic surfactant containing only a polyoxyethylene group as a polyoxyalkylene group) is not sufficient.

In the present invention, when a polyvinyl alcohol-based film is actually produced, it is characterized in that it contains more nonionic surfactant than the usual content of a surfactant which is usually used to improve film formability. The nonionic surfactant also has an oxypropylene group that is not used.

The present invention also provides a method for producing a polyvinyl alcohol-based film, which comprises 1 to 20 parts by weight of an oxyethylene group and an oxypropylene group-containing nonionic system based on 100 parts by weight of the polyvinyl alcohol-based resin (A). A method in which a polyvinyl alcohol-based resin aqueous solution obtained by using a surfactant (B) is cast and formed into a film.

Furthermore, the present invention provides a laminate for transfer, comprising a base film [I] composed of the polyvinyl alcohol film, a curable resin layer [II], and a printed layer [III].

The polyvinyl alcohol-based film of the present invention contains a surfactant which has a larger amount of "not only an oxyethylene group but also an oxypropylene group as an oxygen-extended alkyl group" as compared with the prior art, and therefore has a very excellent release. Sex. Therefore, it can be used for applications such as separators or protective films that require mold release. Further, it can be used as a base film of the transfer laminated body used for heat transfer without interposing the release agent layer.

[Polyvinyl alcohol film]

First, the polyvinyl alcohol-based film of the present invention will be described.

The polyvinyl alcohol-based film of the present invention is obtained by including a nonionic surfactant (B) having an oxyethylene group and an oxypropylene group in the polyvinyl alcohol-based resin (A).

(1) Polyvinyl alcohol resin (A)

The polyvinyl alcohol-based resin (A) used in the present invention is obtained by polymerizing a vinyl ester-based compound according to a conventional method and then saponifying it. In the present invention, the polyvinyl alcohol-based resin (A) may be used alone or in combination of two or more kinds as needed.

Examples of the vinyl ester-based compound include vinyl formate, vinyl acetate, vinyl trifluoroacetate, vinyl propionate, vinyl butyrate, vinyl phthalate, vinyl laurate, vinyl versatate. ), vinyl palmitate, vinyl stearate, and the like. These may be used alone or in combination of two or more kinds, and vinyl acetate may be preferably used practically.

Further, in the polyvinyl alcohol-based resin (A) used in the present invention, it is generally preferred to use an unmodified polyvinyl alcohol resin, but a partially modified modified polyvinyl alcohol-based resin may also be used. The modified polyvinyl alcohol-based resin may be a copolymer of a vinyl ester-based compound and a small amount of another monomer. In this case, the ratio of the monomer is not inhibited by the effect of the present invention, and is, for example, 10 mol% or less. It is 7 mol% or less.

Examples of the other monomer include ethylene, propylene, isobutylene, α-octene, α-dodecene, and α-octadecene; and acrylic acid, methacrylic acid, crotonic acid, maleic acid, and the like. Maleic anhydride, itaconic acid Such as unsaturated acids or salts thereof, or mono- or dialkyl esters; nitriles such as acrylonitrile and methacrylonitrile; decylamines such as acrylamide and methacrylamide; vinylsulfonic acid and allyl Olefinic acid such as sulfonic acid or methallylsulfonic acid or a salt thereof, alkyl vinyl ether; polyoxyethylene (meth) allyl ether, polyoxypropylene (meth) allyl ether, etc. Oxyalkylene (meth)allyl ether; polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate, etc. polyoxyalkylene (meth) acrylate; polyoxyethylene (A) Polyoxyalkylene (meth) acrylamide such as acrylamide or polyoxypropylene (meth) acrylamide; polyoxyethylene [1-(methyl) acrylamide-1,1-dimethyl Propyl]ester, polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine, polyoxypropylene vinylamine, dipropylene acetone Indoleamine, N-propylene decylamine methyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethyldiallylammonium chloride, dimethylallyl vinyl ketone, N- Vinyl pyrrolidone, vinyl chloride, Vinyl chloride and so on. These other monomers may be used alone or in combination of two or more.

Further, in the present invention, the term "(meth)allyl" means an allyl group or a methallyl group, and the so-called (meth)acryl group means a propenyl group or a methacryl group, and so-called (A) Acrylate, meaning acrylate or methacrylate.

Further, when polymerization (or copolymerization) is carried out using the above vinyl ester-based compound, a known polymerization method can be used without particular limitation, but usually, an alcohol such as methanol, ethanol or isopropyl alcohol is used as a solvent to carry out solution polymerization. Further, emulsion polymerization or suspension polymerization may be carried out in addition to solution polymerization.

Further, the polymerization reaction is carried out by using a known radical polymerization catalyst such as azobisisobutyronitrile, ethylene peroxide, benzammonium peroxide or ruthenium peroxide. The reaction temperature is usually selected from the range of 35 ° C to the boiling point, more preferably about 50 to 80 ° C.

Then, when the obtained vinyl ester polymer is saponified, the vinyl ester polymer is dissolved in an alcohol and carried out in the presence of a basic catalyst. The alcohol may be, for example, methanol, ethanol or butanol, and the concentration of the vinyl ester copolymer in the above alcohol is appropriately selected within the range of 20 to 50% by weight.

As the alkaline catalyst in the above saponification, an alkali catalyst such as a hydroxide or an alcoholate of an alkali metal such as sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide or potassium methoxide can be used. The amount of the basic catalyst to be used may be appropriately selected in the range of 1 to 100 mmol equivalents based on the vinyl ester polymer. Further, saponification may be carried out by an acid catalyst as the case may be.

Thus, a polyvinyl alcohol-based resin (A) can be obtained.

Further, the polyvinyl alcohol-based resin (A) is preferably a polyvinyl alcohol-based resin having a 1,2-glycol bond in a side chain, and the above-mentioned polyvinyl alcohol having a 1,2-glycol bond in a side chain. The resin can be obtained, for example, by (i) a method of saponifying a copolymer of vinyl acetate and 3,4-diethyloxy-1-butene, and (ii) extending vinyl acetate and ethylene carbonate. a method for saponifying and decarboxylating a copolymer of ethyl ester, (iii) saponifying and deketalizing a copolymer of vinyl acetate and 2,2-dialkyl-4-vinyl-1,3-dioxolane And (iv) a method of saponifying a copolymer of vinyl acetate and glycerin monoallyl ether.

In the present invention, the average degree of saponification of the polyvinyl alcohol-based resin (A) is usually 70 mol% or more. For example, in the application of processing at a high temperature of 100 ° C or higher, the average degree of saponification is preferably 70. ~90% by mole, on the other hand, in applications where heat resistance is important, the average degree of saponification is preferably 90. More than Mole. Among them, the average degree of saponification can be appropriately selected from the range of 70 mol% or more depending on the processing conditions or purpose. In addition, when the average degree of saponification of the polyvinyl alcohol-based resin (A) is too low, there is a tendency that not only the film strength is lowered but also the film is peeled off from the casting surface during production.

Further, the above average degree of saponification is measured in accordance with JIS K 6726.

Further, the viscosity of the polyvinyl alcohol-based resin (A) in a 4% by weight aqueous solution at 20 ° C is preferably 5 to 70 mPa. The range of s is more preferably 15~60mPa. The range of s. If the viscosity of the 4% by weight aqueous solution is too low, the strength of the film tends to decrease. On the other hand, if the viscosity of the 4% by weight aqueous solution is too high, the viscosity tends to be high and it is difficult to form a film. Further, the above 4% by weight aqueous solution viscosity at 20 ° C was measured in accordance with JIS K 6726.

(2) Nonionic surfactant (B)

The nonionic surfactant (B) used in the present invention is a structural unit containing an oxyethylene group and an oxypropylene group as an oxygen alkyl group. In general, a surfactant is often added to a polyvinyl alcohol-based film in order to improve the peeling of the drum or the tape on the substrate when the film is self-made, and the roll-wound property. The surfactant to be blended for such a purpose is an oxyethylene group having excellent hydrophilicity as an oxygen-extended alkyl structural unit. The nonionic surfactant (B) used in the present invention is characterized in that it contains an oxyethylene group in the hydrophilic portion and an oxypropylene group in the hydrophobic portion. Usually, the hydrophobic portion contains a long-chain alkyl group, and the adjustment of the hydrophobicity can be adjusted by the length of the alkyl chain or the like, but in the present invention, the nonionic surfactant (B) used is an oxyethylene group and The proportion of the oxypropylene group is adjusted.

Nonionic boundary of structural units containing both oxyethylene and oxypropylene groups Examples of the surfactant (B) include an alkyl ether (B1) to which an aerobic vinyl group and an oxypropylene group are added, a fatty acid ester (B2) to which an aerobic vinyl group and an oxypropylene group are added, and an addition compound. Oxyethylene group and oxypropylene group polyol ether (B3), addition of aerobic vinyl group and oxypropylene group alkyl phenyl ether, addition of aerobic vinyl group and oxypropylene group polyol ester, etc. At least one of these. Among these, in terms of mold release effect and availability, it is preferred to add an alkyl group (B1) of an aerobic vinyl group and an oxypropylene group, an alkoxy group and an oxypropylene group. Fatty acid ester (B2), addition of aerobic vinyl and oxypropylene based polyol ether (B3), especially addition of aerobic vinyl and oxypropylene based alkyl ether (B1), addition aerobic Vinyl and oxypropylene based polyol ethers (B3).

Examples of the above-mentioned alkyl ether (B1) to which an aerobic vinyl group and an oxypropylene group are added include polyoxyethylene polyoxypropylene alkyl ethers, and specific examples thereof include polyoxyethylene polyoxypropylene butyl ether and polyoxyethylene. Polyoxypropylene oxime ether, polyoxyethylene polyoxypropylene lauryl ether, polyoxyethylene polyoxypropylene myristyl ether, polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene stearyl ether, polyoxyethylene Polyoxypropylene oleyl ether and the like.

Examples of the above-mentioned fatty acid ester (B2) to which an aerobic vinyl group and an oxypropylene group are added include polyoxyethylene polyoxypropylene alkyl esters, and specific examples thereof include polyoxyethylene polyoxypropylene laurate.

Examples of the above-mentioned polyol (B3) to which an aerobic vinyl group and an oxypropylene group are added include polyoxyethylene polyoxypropylene polyol ethers, and specific examples thereof include polyoxyethylene polyoxypropylene glyceryl ether and polyoxyethylene. Polyoxypropylene diglyceryl ether, polyoxyethylene polyoxypropylene sorbitol ether, and the like.

The above-mentioned addition of an alkoxyphenyl group of an aerobic vinyl group and an oxypropylene group, for example, Specific examples of the polyoxyethylene polyoxypropylene alkyl phenyl ethers include polyoxyethylene polyoxypropylene hexyl phenyl ether, polyoxyethylene polyoxypropylene heptyl phenyl ether, polyoxyethylene polyoxypropylene octyl phenyl ether, and the like. .

Examples of the above-mentioned polyol ester to which an aerobic vinyl group and an oxypropylene group are added include polyoxyethylene polyoxypropylene sorbitan fatty acid esters.

In the present invention, the number of structural units of the oxyethylene group in the nonionic surfactant (B) is preferably from 1 to 70, particularly preferably from 2 to 60, more preferably from 4 to 50. When the number of the structural units is too large, the viscosity of the polyvinyl alcohol-based resin aqueous solution tends to increase, and the planar smoothness of the obtained film tends to be lowered. Further, the number of structural units of the oxypropylene group in the nonionic surfactant (B) is preferably from 1 to 70, particularly preferably from 2 to 60, more preferably from 4 to 50. When the number of the structural units is too large, the viscosity of the polyvinyl alcohol-based resin aqueous solution tends to increase, and the planar smoothness of the obtained film tends to be lowered. Further, the total number of structural units of the oxyethylene group and the number of structural units of the oxypropylene group is preferably 2 to 100, more preferably 4 to 85, still more preferably 6 to 80, most preferably 20 to 80. When the number of the structural units is too large, the viscosity of the polyvinyl alcohol-based resin aqueous solution tends to increase, and the planar smoothness of the obtained film tends to be lowered.

When the surfactant (B) contains a plurality of oxyethylene groups and oxypropylene groups, it may be one in which an oxyethylene unit and an oxypropylene unit block are copolymerized or randomly copolymerized. However, in order to allow the oxyethylene group to function as a hydrophilic portion and to function sufficiently as a hydrophobic portion, the oxypropylene group is preferably present as a polyoxyethylene moiety and a polyoxypropylene moiety, so that the surfactant is more Good is a block copolymer.

Further, in the present invention, the ratio of the oxyethylene group to the oxypropylene group (oxyethylene group/oxypropylene group) (mole ratio) in the nonionic surfactant (B) is increased in mold release property. In terms of aspect, it is preferably 90/10 to 10/90, particularly preferably 80/20 to 20/80, and further preferably 70/30 to 30/70. When the content ratio of the oxyethylene group to the oxypropylene group is too small or too large, the mold release property to the curable resin layer tends to decrease.

Further, in the present invention, the weight average molecular weight of the nonionic surfactant (B) is preferably from 100 to 10,000, particularly preferably from 200 to 8,000, in terms of an increase in mold release property or an accuracy of viscosity. When the weight average molecular weight is too small, the mold release property tends to be lowered. When the weight average molecular weight is too large, the viscosity of the polyvinyl alcohol resin aqueous solution increases, which tends to cause failure during film production.

In the present invention, the HLB of the nonionic surfactant (B) is preferably from 2 to 18, particularly preferably from 2 to 15, more preferably from 3 to 12, in terms of mold releasability. In the present invention, the HLB value is a value calculated by the Griffin method and is calculated by the following formula.

HLB = 20 × (molecular weight of hydrophilic part / molecular weight of whole)

Here, the hydrophilic portion means a total molecular weight mainly composed of oxyethylene structural units. Therefore, it is preferred that the HLB value of the ratio of the oxyethylene structural unit to all the molecules of the surfactant (B) is in the above range. The surfactant (B) having an HLB value in the above range means that it has a balance of moderate hydrophobicity within a range which does not impair the dispersibility in water. It is considered that by having such a balance, good dispersibility in a polyvinyl alcohol-based resin is ensured, and it is easily permeable to a polyvinyl alcohol-based film by an improved hydrophobicity. Out of the state. The surfactant (B) which bleeds out on the surface of the polyvinyl alcohol-based film can function as one type of release agent. Therefore, it is presumed to be used as a base film for a laminate for heat transfer, which contributes to hardening after transfer. The peeling of the resin layer and the base film is improved.

In the present invention, the content of the nonionic surfactant (B) is preferably from 1 to 20 by weight based on 100 parts by weight of the polyvinyl alcohol resin (A) in terms of mold release property and film appearance. The portion is further preferably 2 to 15 parts by weight, particularly preferably 3 to 10 parts by weight, most preferably 5 to 8 parts by weight. In general, the amount of the surfactant added to improve the mold release property of the drum or the belt which becomes the substrate at the time of film formation is less than 1 part by weight based on 100 parts by weight of the polyvinyl alcohol resin, and thus the polyvinyl alcohol of the present invention is The film is characterized by more than the usual amount. The reason for this is that the nonionic surfactant (B) used in the present invention is contained as an additive in order to obtain an effect of improving mold release property caused by exudation of the nonionic surfactant (B). The amount is not sufficient. On the other hand, when the content is too large, the amount of the nonionic surfactant (B) which permeates the surface increases, and the surface of the film tends to become sticky. As a result, in the case where other resins are laminated on the film, there are cases where other resins are repelled. In the case where the above-described case is used as a base film for a laminate for heat transfer, the surface properties of the transfer layer are lowered due to the possibility of repelling the cured resin of the layer, and the surface gloss of the protective layer of the obtained molded article is further improved. The reason for the decrease.

(3) Other ingredients

The polyvinyl alcohol-based film of the present invention is not limited to a composition containing only the polyvinyl alcohol-based resin (A) and the nonionic surfactant (B). A polyethylene-based alcohol film produced. It is also preferably produced by suitably blending a surfactant (B') other than the nonionic surfactant (B) or a plasticizer. Further, the filler may be blended within the scope of the object of the present invention.

(3-1) Other interface forming agent (B')

In order to improve the release property of the film surface of the film formed by the film forming device of the polyvinyl alcohol film and the release film, the interface activity other than the above nonionic surfactant (B) is blended. Agent (hereinafter referred to as "other surfactant (B')").

The other surfactant (B') may, for example, be a surfactant other than the above-mentioned nonionic surfactant containing an oxyethylene group and an oxypropylene group as a nonionic surfactant, for example, only an oxyethylene group Or polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene alkyl esters, sorbitan fatty acid esters, polyoxygen extensions Alkyl alkylamines, polyoxyalkylene alkyl decylamines, polypropylene glycol ethers, acetylene glycols, allyl phenyl ethers, and the like.

Further, the other surfactant (B') is not limited to the nonionic surfactant, and an anionic surfactant, a cationic surfactant, or an amphoteric surfactant may be used. The anionic surfactant is preferably a carboxylic acid type such as potassium laurate or a sulfate type such as octyl sulfate or a sulfonic acid type anionic surfactant such as dodecylbenzenesulfonate. Examples of the cationic surfactant include an amine such as laurylamine hydrochloride, a quaternary ammonium salt such as lauryl trimethylammonium chloride, or a pyridinium salt such as laurylpyridinium chloride. As the amphoteric surfactant, for example, N-alkyl-N,N-dimethylammonium beet Alkali, etc.

The other surfactants (B') may be used alone or in combination of two or more.

The content of the other surfactant (B') may be as long as it does not impair the object of the present invention, and may be any degree as long as it does not have bleed out, for example, the surface property such as surface whitening is lowered, usually with respect to polyethylene. 100 parts by weight of the alcohol resin is 1 part by weight or less.

(3-2) Plasticizer

Examples of the plasticizer include glycerol such as glycerin, diglycerin or triglycerin; an alkanediol such as triethylene glycol, polyethylene glycol, polypropylene glycol or dipropylene glycol; or trimethylolpropane. These may be used alone or in combination of two or more.

The blending amount of the plasticizer to be blended in the polyvinyl alcohol-based resin (A) is preferably 30 parts by weight or less, and particularly preferably 20 parts by weight, based on 100 parts by weight of the polyvinyl alcohol-based resin (A). the following. When the blending amount of the plasticizer is too large, the toughness of the film gradually disappears and it tends to be difficult to handle. Further, the lower limit of the plasticizer is usually 0.5 part by weight.

(3-3) filler

Examples of the filler include starch (not only various unprocessed products but also etherified, oxidized or modified products) or organic powders such as polymethyl methacrylate; inorganic powders such as talc, mica and cerium oxide; . These may be used alone or in combination of two or more. Among them, starch can be preferably used.

The blending amount of the filler to be blended in the polyvinyl alcohol-based resin (A) is preferably 20 parts by weight or less, and particularly preferably 15 parts by weight or less based on 100 parts by weight of the polyvinyl alcohol-based resin (A). When the blending amount of the above filler is too large, the film strength tends to decrease in practical use.

(3-4) Other additives

Further, insofar as the effects of the present invention are not impaired, an antioxidant (phenol type, amine type, etc.), a stabilizer (phosphate type, etc.), a coloring material, a fragrance, an extender, an antifoaming agent, and the like may be appropriately blended. A rust preventive, an ultraviolet absorber, and further blendable with other water-soluble polymer compounds (sodium polyacrylate, polyoxyethylene, polyvinylpyrrolidone, dextrin, polyglucamine, chitin, methyl cellulose, Other additives such as hydroxyethyl cellulose and the like.

Since the polyvinyl alcohol-based film of the present invention having the above-described structure is excellent in mold release property, when used as a film for heat transfer, the release agent is not interposed between the curable resin layer and the polyvinyl alcohol film. In the layer, the curable resin layer (protective layer) transferred to the surface of the molded article can be easily peeled off from the polyvinyl alcohol-based film of the base film after heat transfer.

Further, although the polyvinyl alcohol-based film of the present invention imparts excellent mold release properties as described above, it can maintain the properties of the polyvinyl alcohol-based film, that is, hydrophilicity, water solubility, organic solvent resistance, and gas barrier. It is not limited to the base film of the laminate for thermal transfer, and can be used as a base film for a laminate for hydraulic transfer, and can be used as a polyvinyl alcohol film for other purposes. For other previously known uses.

[Method for Producing Polyvinyl Alcohol Film]

Hereinafter, a method for producing the polyvinyl alcohol-based film of the present invention will be described.

First, the polyvinyl alcohol-based resin (A), the nonionic surfactant (B), optionally other surfactant (B'), a plasticizer, other additives, and the like are blended in a specific blending amount. Combine dissolved in water to prepare a poly A vinyl alcohol resin aqueous solution.

The concentration of the aqueous solution of the polyvinyl alcohol-based resin is usually preferably from 10 to 30% by weight, particularly preferably from 15 to 25% by weight. When the concentration is too low, the stability of the film thickness tends to decrease, and if it is too high, the viscosity tends to be high and the film formation tends to be difficult.

Then, the polyvinyl alcohol-based resin aqueous solution is cast from a T-die on a film-forming tape or a film-forming drum and dried to form a film, and if necessary, heat-treated, thereby producing.

Here, the film forming tape refers to an endless belt which is stretched between a pair of rolls and moves, and the polyvinyl alcohol-based resin aqueous solution which flows out from the T mold is cast and dried on the endless belt. The endless belt is preferably made of, for example, stainless steel, and the outer peripheral surface thereof is subjected to mirror polishing.

In addition, the above-mentioned film-forming drum is a drum-type roll which is rotated, and the polyvinyl alcohol-based resin aqueous solution which flows out from the T-molding mold is cast and dried on one or more rotating drum rolls.

The drying temperature is usually preferably from 80 to 160 ° C, particularly preferably from 90 to 150 ° C, in the case of using a film-forming tape. When the drying temperature is too low, the drying tends to be insufficient, and the peeling from the belt tends to be sluggish. If the drying temperature is too high, the water content tends to be too low and the film tends to become brittle.

Further, in the case of using a film forming drum, the first film forming film is usually preferably 80 to 100 ° C, particularly preferably 82 to 99 ° C. When the drying temperature is too low, the drying tends to be insufficient, and the peeling from the drum tends to be retarded. If the drying temperature is too high, the water content tends to be too low and the film tends to be brittle. Here, the first film forming film refers to a flow of a polyvinyl alcohol-based resin aqueous solution which flows out from the T mold. The drum type roller is located on the most upstream side.

After the above drying, heat treatment is carried out as needed, and examples of the heat treatment include a heat roll (including a roll), hot air, far infrared ray, and dielectric heating. Further, the surface to be heat-treated is preferably the surface on the opposite side to the surface in contact with the film forming tape or the film forming drum. Further, the water content of the film subjected to the heat treatment is usually preferably about 4 to 8% by weight. Further, the water content of the film after the heat treatment is usually preferably from 2 to 6% by weight.

In addition, the water content of the polyvinyl alcohol-based film can be measured, for example, using a card-charge moisture meter ("MKS-210" manufactured by Kyoto Electronics Manufacturing Co., Ltd.).

The heat treatment by the above heat treatment machine is usually preferably carried out at 50 to 130 ° C, more preferably 60 to 120 ° C. In other words, when the temperature of the heat treatment is too low, the surface which is in contact with the film forming tape or the film forming first drum tends to curl, which makes it difficult to handle. If the temperature of the heat treatment is too high, the film becomes soft. When the winding and stretching were carried out without wrinkles, the alignment in the longitudinal direction was enhanced and the width was reduced. Further, in the case of the heat treatment roll, the time required for the heat treatment depends on the surface temperature, but is usually 0.2 to 15 seconds, preferably 0.5 to 12 seconds. The above heat treatment is usually carried out after treatment with a drying roll for film drying, usually by a heat treatment roll or a floating dryer or the like.

A polyvinyl alcohol-based film can be obtained in this manner.

The film thickness of the polyvinyl alcohol-based film of the present invention is preferably from 15 to 100 μm, particularly preferably from 20 to 80 μm.

The water content of the polyvinyl alcohol-based film obtained above is preferably in the range of 0.5 to 8% by weight, more preferably 1 to 6% by weight. If the water content is too low, then save In the tendency to become brittle, if the water content is too high, there is a tendency to stick.

The method of adjusting the water content of the polyvinyl alcohol-based film may, for example, be the method described below. In other words, the water content of the polyvinyl alcohol-based film within the above range can be set according to the water content adjusting method shown below.

(i) The method of adjusting the moisture content by drying the polyvinyl alcohol-based resin aqueous solution and changing the temperature of the dryer when the film is formed, thereby performing humidification and dehumidification of the polyvinyl alcohol-based film. Since the temperature of the aqueous resin solution affects the drying efficiency depending on the temperature, it is adjusted in the range of 70 to 98 °C. Further, in the case of drying, it is preferably carried out in a hot air dryer having a temperature gradient of between 150 and 50 ° C, more preferably between 145 and 60 ° C, and further, from the viewpoint of moisture adjustment. Preferably, it takes 1 to 12 minutes for drying, and more preferably 1 to 11 minutes for drying.

If the gradient of the drying temperature is too large or the drying time is too long, the drying tends to be excessive. On the contrary, if the gradient of the drying temperature is too small or the drying time is too short, drying tends to be insufficient.

The above temperature gradient is between 150 and 50 ° C, and the drying temperature is changed stepwise, and it is usually effective to gradually raise the temperature from the start of drying to reach the maximum drying temperature in the temporarily set drying temperature range until the specific water content is reached. The rate is then lowered, and then the drying temperature is slowly lowered, thereby finally achieving the target moisture content. It is carried out in order to control crystallinity, mold release property, productivity, etc., for example, 120 ° C - 130 ° C - 115 ° C - 100 ° C, 130 ° C - 120 ° C - 110 ° C, 115 ° C - 120 ° C - 110 ° C A temperature gradient of -90 ° C is set and implemented as appropriate.

(ii) The moisture content is adjusted by humidifying and dehumidifying the polyvinyl alcohol film by passing through the humidity control tank before the winding of the polyvinyl alcohol film.

(iii) The moisture content is adjusted by heat-treating the polyvinyl alcohol-based film before or after the coiling of the polyvinyl alcohol-based film.

Moreover, the polyvinyl alcohol-based film of the present invention may be provided with a concave-convex pattern such as a satin pattern, an embossed pattern, or a crepe pattern as needed, and the uneven pattern may be formed using an embossing roll or the like.

Further, the polyvinyl alcohol-based film of the present invention can be used as an unstretched film as it is for various purposes, and can also be used as a uniaxially stretched or biaxially stretched film.

In the case of being used as a stretched film, the stretching method can be applied to a known method, and the usual methods include, for example, (1) chuck-type stretching, (2) roll stretching, and (3) tenter type. Stretching, etc. (1) It is suitable for the production of a stretched film of a batch type, and (2) is suitable for uniaxial stretching. Moreover, although the apparatus becomes expensive, (3) it is effective for producing a stretched film on an industrial scale. Biaxial stretching can also be carried out successively by combining (2) and (3). The stretching method may be any one of uniaxial stretching, sequential biaxial stretching, and simultaneous biaxial stretching, wherein in terms of uniformity of film thickness, combinations (2) and (3) are preferred. Biaxial stretching.

The stretched film preferably has a total draw ratio of from 1.5 to 16 times, more preferably from 2 to 12 times, and still more preferably from 3 to 10 times, in terms of surface uniformity of the film. Alternatively, in terms of film surface uniformity, the stretching ratio can be preferably applied by stretching 1.5 to 10 times, particularly 2 to 8 times, and further 3 to 5 times in the longitudinal direction, and stretching in the transverse direction by 1.5. ~10 times, especially 2~8 times, and then 3~5 times. In the case of biaxial stretching, in terms of film surface uniformity, It is preferably stretched 1.5 to 4 times, particularly 2 to 3.5 times in the longitudinal direction, and 1.5 to 4 times, especially 2 to 3.5 times, in the transverse direction, and more preferably in the vertical and horizontal directions. When the draw ratio is too low, there is a tendency that the stretching unevenness tends to remain, and when the draw ratio is too high, the film tends to be easily broken.

For the storage of the polyvinyl alcohol-based film, for example, it is preferably subjected to a conventionally known moisture-proof packaging treatment, and stored in a suspended state in an environment of 10 to 25 °C.

[Laminated body for thermal transfer]

The layered body for thermal transfer of the present invention is a layered base film [I], a curable resin layer [II], and a printed layer [III].

(1) Basement membrane [I]

As the base film [I], the above polyvinyl alcohol-based film of the present invention can be used. For the polyvinyl alcohol-based film, an unstretched film can be used as it is, or as a uniaxially stretched or biaxially stretched film.

In the present invention, the thickness of the base film [I] is particularly preferably in the range of 5 to 120 μm, more preferably 10 to 100 μm.

Further, in the present invention, the surface roughness (Ra) of the curable resin layer [II] side of the base film [I] is preferably 1 μm or less, and particularly preferably 0.001 to 0.7, in terms of surface glossiness. Μm, further preferably 0.01 to 0.5 μm. If the surface roughness (Ra) is too large, the surface gloss tends to be lowered. Further, there is a tendency that even if the surface roughness (Ra) is less than 0.001 μm, the tendency to improve the surface glossiness is hardly observed. In the base film [I], the surface roughness (Ra) of the side of the curable resin layer [II] is adjusted. In the method of the above range, the surface roughness of the casting tape when the base film [I] is formed is 1 S or less, or the stretching ratio at the time of film formation of the base film [I] is at least 1.5 times. The above method, or a method of combining the two, and the like.

In addition, the surface roughness (Ra) was obtained by using the "color 3D laser microscope VK-9700" manufactured by Keyence Co., Ltd., and measuring the arithmetic mean roughness (Ra) in accordance with JIS B 0601-2001.

(2) Curable resin layer [II]

The curable resin layer [II] is a layer which is the outermost layer of the decorative molded article by the peeling of the base film [I], and is cured during the period before or after peeling off the base film [I]. A protective layer that protects the surface of the transferred body.

The material constituting the curable resin layer [II] may, for example, be a thermoplastic resin such as a polyacrylic resin, a polyester resin, a polyvinyl chloride resin, a cellulose resin, a rubber resin, a polyurethane resin or a polyvinyl acetate resin. Resin; an active energy ray-curable resin composition such as an ultraviolet curable resin composition or an electron beam curable resin composition; a thermosetting resin composition or the like. As the protective layer, from the viewpoint of imparting chemical resistance and abrasion resistance, it is preferred to use an active energy ray-curable resin composition.

The active energy ray-curable resin composition is preferably composed of, for example, an acrylic resin or an (meth) acrylate-based compound.

Examples of the acrylic resin include a homopolymer or a copolymer of an acrylate monomer, or an acrylic copolymer having a copolymerizable component of another ethylenically unsaturated monomer.

Examples of the acrylate-based monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. Ethyl acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid Methylaminoethyl ester, isooctyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, 2-methoxyethyl (meth)acrylate, (methyl) Butyloxyethyl acrylate, methoxytriethylene glycol (meth) acrylate, etc., among them, an alkyl acrylate having an alkyl group having 1 to 12 carbon atoms is preferred, and it is preferably used (methyl). ) Methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate.

Examples of the other ethylenically unsaturated monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, and (methyl). ) tetrahydrofurfuryl acrylate, 2-hydroxy 3-phenoxypropyl (meth) acrylate, diethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, N-methylol a hydroxyl group-containing unsaturated monomer such as (meth)acrylamide; a glycidyl group-containing unsaturated monomer such as glycidyl methacrylate or glycidyl methacrylate; and 2-acrylonitrile isocyanate Isocyanate group-containing unsaturated monomer such as oxyethyl ester or 2-methylpropenyloxyethyl isocyanate; acrylamide, methacrylamide, N-(n-butoxyalkyl)propene oxime An amidino group-containing unsaturated monomer such as an amine or N-(n-butoxyalkyl)methacrylamide; acrylamide-3-methylbutylmethylamine, dimethylaminoalkyl acrylamide, and An amino group-containing unsaturated monomer such as methylaminoalkylmethyl acrylamide; an olefin sulfonic acid such as vinyl sulfonic acid, allyl sulfonic acid or methallyl sulfonic acid; -Methylpropanesulfonic acid, phenylethyl Unsaturated monomers containing sulfonic acid or a salt of a sulfonic acid group; styrene, vinyl acetate, acrylonitrile, acrylamide and the like.

The content ratio (copolymerization ratio) of the acrylate monomer and the other ethylenically unsaturated monomer is not particularly limited. For example, the acrylate monomer is preferably 20 to 100% by weight, and the other ethylenicity is not The saturated monomer is preferably 0 to 80% by weight, more preferably 40 to 100% by weight of the acrylate monomer, and 0 to 60% by weight of the other ethylenically unsaturated monomer, and more preferably acrylic acid. The ester monomer is 80 to 100% by weight, and the other ethylenically unsaturated monomer is 0 to 20% by weight. When the content ratio of the acrylate-based monomer is too small, the cured product (protective layer) of the curable resin layer tends to have poor durability such as water resistance and moist heat resistance.

The acrylic resin can be easily produced by, for example, subjecting the above-mentioned polymerization component to radical copolymerization in an organic solvent according to a method known to a person skilled in the art.

The acrylic resin used in the active energy ray-curable resin composition preferably has a glass transition temperature (Tg) of 20 to 130 ° C, more preferably 30 to 120 ° C, still more preferably 40 to 110 ° C. When the glass transition point (Tg) is too low, the curable resin layer such as the active energy ray-curable resin composition has adhesiveness and is defective in the subsequent processing (also curling and poor printing in the step). When the tendency is high, the curable resin layer such as the active energy ray-curable resin composition is cured to form a protective layer, which tends to become brittle.

Further, the weight average molecular weight (Mw) of the acrylic resin is preferably from 10,000 to 500,000, more preferably from 20,000 to 100,000, still more preferably from 30,000 to 80,000.

If the weight average molecular weight (Mw) of the acrylic resin is too small, then There is a tendency that the curable resin layer before softening is softened and has adhesiveness, so that it causes a problem (for curling in the step, poor printing, etc.) when performing subsequent processing on the layer, if it is too large There is a tendency that the film thickness uniformity in the case where the curable resin layer is applied is difficult to obtain and the hardness of the coating film after drying becomes high above the desired one, which causes a problem in the subsequent processing (the turtle which produces the coating film) Causes of cracking, interlayer peeling, etc.).

The (meth) acrylate-based compound is a (meth) acrylate-based compound having an amine ester bond in the molecule, and a hydroxyl group-containing (meth)acrylic compound and a polyvalent isocyanate compound, and optionally a polyol can be used. It is produced by carrying out a reaction.

Examples of the hydroxyl group-containing (meth)acrylic compound include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. 4-hydroxybutyl methacrylate, 6-hydroxyhexyl (meth) acrylate, 2-(meth) propylene methoxyethyl 2-hydroxypropyl phthalate, (meth) acrylate 2 -Hydroxy-3-(methyl)propenyl propyl propyl ester, caprolactone modified 2-hydroxyethyl (meth) acrylate, neopentyl alcohol tri (meth) acrylate, dipentaerythritol (Meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, oxyethylene modified dipentaerythritol Alcohol penta (meth) acrylate, oxyethylene modified pentaerythritol tri (meth) acrylate, etc., wherein a hydroxyl group-containing (meth)acrylic acid group having three or more acryl fluorenyl groups can be preferably used. Compound. Further, these may be used alone or in combination of two or more.

Examples of the polyvalent isocyanate compound include an aromatic system. Examples of the polyisocyanate such as an aliphatic or alicyclic system include toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, and modified diphenyl group. Methane diisocyanate, hydrogenated dimethyl diisocyanate, benzodimethyl diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, tetramethyl dimethyl diisocyanate, isophorone Polyisocyanate such as diisocyanate, norbornene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, phenyl diisocyanate, leucine diisocyanate, isocyanuric acid triisocyanate, naphthalene diisocyanate or the like a trimeric compound or a multimeric compound of a polyisocyanate; a biuret type polyisocyanate, a water-dispersible polyisocyanate (for example, "Aquanate 100", "Aquanate 110", "Aquanate 200" manufactured by Nippon Polyurethane Industry Co., Ltd. "Aquanate 210" or the like), or a reaction product of the polyisocyanate and a polyhydric alcohol.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, and polybutylene glycol. 6-hexanediol, neopentyl glycol, cyclohexanedimethanol, hydrogenated bisphenol A, polycaprolactone, trimethylolethane, trimethylolpropane, polytrimethylolpropane, neopentyl Polyols such as alcohol, polytetramethylene glycol, sorbitol, mannitol, glycerin, polyglycerol, polyether diol, polyoxyethylene, polyoxypropylene, block with oxyethylene/oxypropylene or random copolymerization a polyether polyol having at least one structure; the polyol or polyether polyol with maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, Polyester polyol of a condensate of a polybasic acid such as isophthalic acid; A caprolactone-modified polyol such as an ester-modified polyether polyol; a polyolefin-based polyol; a polybutadiene-based polyol such as a hydrogenated polybutadiene polyol;

Further, examples of the polyhydric alcohol include 2,2-bis(hydroxymethyl)butyric acid, tartaric acid, 2,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, and 2,2-bis(hydroxyl). Methyl)propionic acid, 2,2-bis(hydroxyethyl)propionic acid, 2,2-bis(hydroxypropyl)propionic acid, dihydroxymethylacetic acid, bis(4-hydroxyphenyl)acetic acid, 4, a carboxyl group-containing polyol such as 4-bis(4-hydroxyphenyl)pentanoic acid or uronic acid; or a sulfonic acid group or a sulfonic acid base-containing polyol such as sodium 1,4-butanediol sulfonate.

In the case of using a reaction product of a polyisocyanate and a polyhydric alcohol, for example, it may be used as a polyisocyanate having an isocyanate group at the terminal obtained by reacting the above polyol with the above polyisocyanate. In the reaction of the polyisocyanate with the polyol, in order to promote the reaction, it is also preferred to use a metal catalyst such as dibutyltin dilaurate or, for example, 1,8-diazabicyclo[5.4.0]undecene-7. The amine is a catalyst or the like.

The method for producing the (meth)acrylic acid amine ester compound may, for example, be a method in which a hydroxyl group-containing (meth)acrylic compound and a polyvalent isocyanate compound are mixed in an inert gas atmosphere, and are usually reacted at 30 to 80 ° C. ~10 hours method. In the reaction, an amine esterification catalyst such as tin octenate, di-n-butyltin dilaurate, lead octoate, potassium octylate, potassium acetate, stannous octoate or triethylenediamine is preferably used.

The weight average molecular weight of the (meth) acrylate-based compound is preferably from 300 to 4,000, more preferably from 1,000 to 3,500, still more preferably from 1,200 to 3,000. When the weight average molecular weight is too small, the cohesive force tends to be insufficient after the hardening-curable resin layer, and if it is too large, the viscosity is too high. The tendency to be difficult to manufacture.

In addition, the weight average molecular weight is a weight average molecular weight in terms of a molecular weight of a standard polystyrene, and is used by a high performance liquid chromatography ("Shodex GPC system-11 type" manufactured by Showa Denko Co., Ltd.). 3 columns in series: Shodex GPC KF-806L (excluding the limit molecular weight: 2 × 10 ⁷ , separation range: 100 ~ 2 × 10 ⁷ , theoretical number of plates: 10,000 plates / root, filler material: styrene - diethylene The benzene copolymer, filler particle size: 10 μm) was measured.

In this manner, an active energy ray-curable resin composition containing an acrylic resin and a (meth) acrylate-based compound can be obtained. However, when the active energy ray-curable resin composition is an ultraviolet curable resin composition, It is preferred to further contain a photopolymerization initiator. In the case of an electron beam curable resin composition, a photopolymerization initiator is not required.

Examples of the photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 4-(2). -hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholinyl (4-thiomethylphenyl) Propane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone, 2-hydroxy-2-methyl-1-[4-(1-A Acetophenones such as phenyl) phenyl]acetone oligomers; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin; benzophenone, benzoyl benzoic acid Methyl ester, 4-phenylbenzophenone, 4-benzylidene-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl) Benzophenone, 2,4,6-trimethylbenzophenone, 4-benzylidene-N,N- Dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzoammonium bromide, 4-(benzylidenebenzyl)trimethylammonium chloride, etc. Benzophenones; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthiaxanone, 2,4-dichlorothiazepinone, 1- Chloro-4-propoxythiazinone, 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thiaxanthone-9-one meso chloride Isothioxanthone; 2,4,6-trimethylbenzimidyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-tri A mercaptophosphine oxide such as methyl-pentylphosphine oxide or bis(2,4,6-trimethylbenzylidene)-oxyphenylphosphine. In addition, these photopolymerization initiators may be used alone or in combination of two or more.

Moreover, the auxiliary agents may also be used in combination: triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (micilenone), 4,4'-diethylaminodiphenyl Methyl ketone, 2-dimethylaminoethyl benzoic acid, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (n-butoxy)ethyl ester, 4-dimethylaminobenzoic acid Isoamyl ester, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethyl 9-oxosulfur (2,4-diethyl thioxanthone), 2,4-diisopropyl 9-oxosulfur (2,4-diisopropyl thioxanthone) and the like.

Among these, it is preferred to use benzyldimethylketal, 1-hydroxycyclohexyl phenyl ketone, benzamidine isopropyl ether, 4-(2-hydroxyethoxy)-phenyl (2-hydroxyl) 2-propyl) ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one.

In the present invention, the thickness of the curable resin layer [II] is preferably from 1 to 150 μm, particularly preferably from 2 to 120 μm, and more preferably from 2 to 100 μm, in terms of abrasion resistance and chemical resistance. . If the thickness is too thin, there is wear resistance When the tendency to reduce the chemical resistance or the chemical resistance is too large, the release film after the transfer tends to be inferior and becomes a cause of burrs or the like.

When the curable resin layer [II] is formed, a coating method such as a gravure coating method, a roll coating method, a bar coating method, a knife coating method, or a lip coating method; a gravure printing method or a web The raw material resin or the raw material resin composition may be laminated by a printing method such as a printing method.

When the active energy ray-curable resin composition is used, a layer composed of an active energy ray-curable resin composition (curable resin layer [II]) may be laminated from the base film [I] until printing The active energy ray is irradiated to the layer [III] at any stage during the period in which the layer [III] is transferred to the transferred body and the base film [I] is peeled off, or the active energy ray may be irradiated to be hardened after the base film [I] is peeled off. And made a protective layer (hard coating).

For example, it can be carried out by (a) laminating an active energy ray-curable resin composition layer on a base film, and then irradiating the active energy ray to harden it; (b) laminating active energy ray hardening on the base film After the resin composition layer, the following printed layer is formed, and then the active energy ray is irradiated from the base film side to be cured; (c) Further, after the layer is laminated to the following subsequent layer, the active energy ray is irradiated from the base film side. And (b) after the transfer layered body of the present invention is attached to the transferred body, the active energy ray is irradiated from the base film side to be hardened; (e) the transfer layered body of the present invention is subsequently applied After being transferred, the base film is peeled off and irradiated with an active energy ray to harden it. In terms of the followability of the transferred body at the time of heat transfer, it is preferably a method of hardening (d) or (e) after transfer, and particularly preferably a method of (e). Further, the layered body for transfer of the present invention may be supplied as in the above (a) to (c). The layered body in which the curable resin layer is cured is preferably supplied as a layered body containing a curable resin layer before curing as in the above (d) and (e).

When the curable resin layer is cured by irradiation of the active energy ray, the active energy ray can be, for example, light such as far ultraviolet ray, ultraviolet ray, near ultraviolet ray, or infrared ray; electromagnetic waves such as X ray or gamma ray, and other electrons can be used. Beams, proton rays, neutron rays, and the like are advantageously hardened by ultraviolet irradiation in terms of hardening speed, availability of an irradiation device, price, and the like.

The method of hardening by ultraviolet irradiation is to irradiate about 0.01 to 10 J/cm ^{2 with} a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, etc., which emit light in a wavelength region of 150 to 450 nm. Just fine. After ultraviolet irradiation, it is also possible to perform heating as needed to achieve complete hardening.

(3) Printed layer [III]

The printed layer [III] is printed with a layer such as a pattern, and the material of the printed layer is made of a polyethylene resin, a polyamide resin, a polyester resin, an acrylic resin, a polyurethane resin, or a polyvinyl acetal resin. A resin such as a polyesteramine ester resin, a cellulose ester resin or an acid alcohol resin may be used as a binder, and a pigment or dye of a suitable color may be used as a coloring ink for the colorant.

As a method of forming the printed layer [III], a usual printing method such as a lithography method, a gravure printing method, or a screen printing method can be used. In particular, in order to perform multicolor printing or gradient display, a plate printing method or a gravure printing method is preferred.

(4) Next layer [IV]

In the layered system for transfer of the present invention, the base film [I], the curable resin layer [II], and the printed layer [III] are laminated, and it is preferable to laminate the layer [IV] on the printed layer [III].

Next, the layer [IV] is the one in which the above-mentioned laminated body is attached to the transferred body. It suffices that it is formed when the adhesion between the printed layer and the molded article is weak. In the material of the layer [IV], a heat-sensitive or pressure-sensitive resin suitable for the material of the object to be transferred may be used as appropriate, and examples thereof include a polyester resin, an acrylic resin, a polystyrene resin, and a polyfluorene. An amine resin, a chlorinated polyolefin resin, a vinyl chloride-vinyl acetate copolymer resin, a cyclized rubber, a benzofuran-indene resin, or the like.

Next, a method of forming the layer [IV] may be a coating method such as a gravure coating method, a roll coating method, a bar coating method or a doctor blade coating method, or a printing method such as a gravure printing method or a screen printing method. Further, the adhesive layer formed of the above material may be bonded by a lamination method or the like to form an adhesive layer [IV]. Further, the layer [IV] may also serve as the printing layer [III].

The thickness of the subsequent layer [IV] is preferably from 0.5 to 50 μm, particularly preferably from 1 to 40 μm, and more preferably from 2 to 30 μm, in terms of the followability of the adherend. If the thickness is too small, the followability of the adherend at the time of transfer tends to decrease, and if it is too thick, there is a tendency that the cost is increased and it is not economical.

[Method of Using the Thermal Transfer Laminate of the Present Invention: Thermal Transfer Method]

The heat transfer method using the laminate for heat transfer of the present invention will be described.

(1) Method of decorating the transferred body surface

First, the transfer layer of the transfer layer is made to have a transfer layer In the case of the layer [IV], it is the adhesion layer [IV], and when the layer [IV] is not provided, the printing layer [III] is adhered to the transferred body surface. Next, a heat transfer rubber type set under the conditions of a temperature of about 80 to 270 ° C and a pressure of about 490 to 1960 Pa is used by a transfer machine such as a roll transfer machine or a reversible transfer machine having a heat-resistant rubber-like elastic body such as ruthenium rubber. Heat and pressure are applied to the base film [I] side of the laminate for the self-transfer. Thereby, the subsequent layer [IV] or the printed layer [III] is followed by the surface of the transferred body.

After cooling, the curable resin layer [II] is cured by irradiation with an active energy ray or the like to form a protective layer (hard coat layer), and finally the base film [I] is peeled off, and then the base film [I] and the protective layer are protected. The boundary surface of the layer (hardened curable resin layer [II]: hard coat layer) is peeled off to terminate the transfer.

(2) A method of decorating the surface of a resin molded article as a transferred body by a forming synchronous transfer method by injection molding

Next, a method of decorating the surface of the resin molded article as the object to be transferred by the forming simultaneous transfer method by injection molding using the transfer laminated body of the present invention will be described.

First, the transfer laminated body is conveyed to the molding die so that the base film becomes the side of the fixed mold (usually the master mold). The transport for the transfer layer may transport the single-layer transfer layer body one by one, or may intermittently transport the necessary portion of the long layer laminate. In the case of using a laminate for a long strip transfer, the printing layer [III] of the transfer laminated body may be registered with the molding die by using a conveying device having a positioning mechanism. Further, when the transfer laminated body is intermittently conveyed, the position of the transfer laminated body is detected by a sensor, and then fixed by a movable mold (mother mold) and a fixed mold (male mold). In the case of the transfer laminated body, the transfer laminated body can be fixed at the same position at all times, and the positional shift of the printed layer [III] does not occur, which is convenient.

After the molding die is closed, the molten molding resin is ejected from the gate and filled in the mold to form the transferred body. The transfer laminated body is conveyed simultaneously with the formation of the transferred body, and then on the surface of the transferred body.

The molding resin to be a material to be transferred includes a general-purpose resin such as a polystyrene resin, a polyolefin resin, an ABS resin, an AS resin, or an AN resin. Further, a polyphenylene ether-polystyrene resin, a polycarbonate resin, a polyacetal resin, an acrylic resin, a polycarbonate modified polyphenylene ether resin, or a polybutylene terephthalate resin can also be used. General engineering resin such as ultra high molecular weight polyethylene resin or polyfluorene resin, polyphenylene sulfide resin, polyphenylene ether resin, polyarylate resin, polyether phthalimide resin, polyimine resin, liquid crystal polyester Super engineering resin such as resin or polyallyl heat-resistant resin. Further, a composite resin to which a reinforcing material such as glass fiber or inorganic filler is added may be used. The transferred body composed of the resins may be any of transparent, translucent, and opaque. Further, the transferred body may or may not be colored.

After cooling the resin molded article as the object to be transferred, the molding die is opened and the resin molded article is taken out. The peeling strength of the base film and the curable resin layer of the layered product for transfer of the present invention is much smaller than the peeling strength of the transferred body and the transfer layer, so that the method of continuously transporting the laminated body for heat transfer is to release the molded article. The peeling of the curable resin layer and the base film occurs. In the case of transporting the film for heat transfer in a single sheet, it is also possible to simply peel off the base film from the molded article taken out.

Thus, a molded article in which the curable resin layer is the outermost layer can be obtained. When the mold release and take-out are performed, when the hardening of the curable resin layer is not completed, the hardening is terminated. The hardened curable resin layer [II] is a protective layer of the molded article.

The decorative molded article thus obtained is also excellent in surface gloss. Although the reason is not clear, it can be considered that the glossiness can be obtained by the fine unevenness on the surface of the coating film (specifically, the unevenness of 1 μm or less), because it can be separated from the curable resin layer by the base film. Since the exuded surfactant is used, it is possible to prevent the curable resin which has not been hardened from being stretched by the base film when the base film is peeled off, or to suppress the wrinkles of the base film when the curable resin is cured while molding.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples as long as it does not exceed the gist of the invention.

In addition, "parts" and "%" which exist in an example mean a weight basis.

[Measurement Evaluation Method]

(1) Evaluation method of polyvinyl alcohol film

(1-1) Peel strength (g/24mm)

After the polyvinyl alcohol film was allowed to stand in an environment of 23° C. and 50% RH for 24 hours, a scotch tape (Sellotape (registered trademark) LP-24 manufactured by Nichiban) having a width of 24 mm was cut into a length of 10 cm in this environment. The 2 kg roller was reciprocated once and the scotch tape was attached to the air surface of the polyvinyl alcohol film. Next, using a tensile tester, the transparent tape was peeled from the film surface at a speed of 300 mm/sec in a 90-degree direction, and the average load at the time of peeling 30 mm at this time was measured. Heavy as the peel strength.

(1-2) Resistance to blocking

A 100 mm x 100 mm piece was cut from the polyvinyl alcohol film. The surface on the air surface side of the film of the two samples was placed on the side of the casting surface, and the humidity was adjusted at 23 ° C × 60% RH for 24 hours, and then directly from the upper portion at 23 ° C × 60% RH. Place a 500g hammer and place it for another 24 hours. Thereafter, the blocking resistance was evaluated on the basis of the following criteria based on the condition of peeling off the two swatches by hand.

○: The swatches were hardly adhered to each other only to the extent that the film was peeled off and the whole was separated.

△: If you want to grab and lift the same piece, the other piece will fall off to the extent of adhesion.

×: The extent to which the sample is required to peel off the sample, the samples are in close contact with each other.

(2) Evaluation of the laminated body for transfer

<Production of laminated body for transfer>

The polyvinyl alcohol film was used as the base film [I], and the active energy ray-curable resin composition was applied onto the base film [I] by a bar coater so as to have a thickness of 160 μm, and dried at 80 ° C. By 15 minutes, a laminate (α) of a curable resin layer [II] having a thickness of 80 μm was formed on the base film [I].

On the surface of the hardened resin layer [II] of the laminate (α), a printing pattern is used to form a lattice pattern by a gravure printing method to obtain a base film [I]/curable resin layer [II]. / Printed layer [III] constitutes a laminate (β).

Further, the thermocompression bonding layer coating was applied to the printed layer [III] of the laminate (β) by a bar coater so as to have a thickness of 100 μm. The cloth liquid was dried at 80 ° C for 15 minutes, thereby forming a thermocompression bonding layer [IV] having a thickness of 20 μm, which was obtained from the base film [I] / curable resin layer [II] / printed layer [III] / The layered body (γ) composed of the layer [IV].

The laminate (γ) and the green glass substrate (thickness: 2.8 mm) were preheated in a dryer heated to 130° C. for 3 minutes to melt the thermocompression bonding adhesive of the laminate (γ), and the hand pressure roller was used to melt the laminate (γ). Next, the layer [IV] surface was pressed against a green glass substrate to prepare a bonded sample.

With respect to the obtained bonded sample, the curable resin layer [II] was cured by irradiating the base film [I] with ultraviolet rays of 1000 mJ to form a protective layer (cured resin layer: hard coat layer). After the protective layer was formed, the protective layer after the base film was peeled off was evaluated in the following manner.

<Evaluation of protective layer>

(2-1) Surface gloss of the protective layer

The fluorescent lamp was reflected on the surface of the protective layer (hardened curable resin layer), and the sharpness of the fluorescent lamp was evaluated by visual observation and based on the following criteria.

○: The outline of the fluorescent lamp is clearly seen.

△: The outline of the fluorescent lamp is blurred.

×: The outline of the fluorescent lamp cannot be confirmed.

(2-2) The writeability of the protective layer

The surface of the protective layer (cured resin layer to be cured) was measured by the following conditions using a writing property measuring apparatus ICM-1DP of a Suga tester, and evaluated based on the following criteria.

(measurement conditions)

Measuring method: reflection

Measuring angle: 45° incident, 45° light receiving

Gap: 0.03mm

Measuring hole: 20mm

Light comb width: 2.0mm

Writeability: C=[(M-m)/(M+m)]×100(%)

C: Write degree (%) at the comb width (mm)

M: the maximum amount of light at the width of the comb (mm)

m: the minimum amount of light at the width of the comb (mm)

(evaluation benchmark)

S: Grade 90% or more

A: Not up to 70~90%

B: Not up to level 30~70%

C: not up to level 30%

[Production and evaluation of polyvinyl alcohol film No. 1-7]

In 100 parts of polyvinyl alcohol (A) having a saponification degree as shown in Table 1 and an average viscosity (20 ° C) of a 4% aqueous solution, the properties shown in Table 1 were blended only in the amounts shown in Table 1 ( a ratio of a content of an oxyethylene group to an oxypropylene group, a weight average molecular weight, a polyalkylene alkyl alkyl ether of HLB), and further, a polyoxyalkylamino ether as a nonionic surfactant (B') B'-1) 0.3 parts of a glycerin as a plasticizer, and a polyvinyl alcohol-based resin aqueous solution (doped) having a solid content concentration of 18% was prepared.

This polyvinyl alcohol-based resin solution was ejected from a T-die to a rotating stainless steel endless belt whose surface temperature was adjusted to 90 ° C, and cast film was formed, and a polyvinyl alcohol film having a thickness shown in Table 1 was obtained. For the obtained polyvinyl alcohol film, based on The above evaluation method evaluated peel strength and blocking resistance. The results are shown in Table 1.

[Production and evaluation of laminates No. 1-7 for transfer]

Using the polyvinyl alcohol film No. 1-7 produced above as the base film [I], a layered product for transfer was produced based on the method for producing the layered product for transfer, and the surface glossiness and imageability were evaluated based on the above evaluation method. . The results are shown together in Table 1.

Further, the active energy ray resin composition constituting the curable resin layer [II], the design printing ink used in the printing layer [III], and the coating for the adhesive layer used in the subsequent layer [IV] were prepared as follows. liquid.

(1) Active energy ray-curable resin composition

40 parts of the solid component of the urethane amide "UV-3520" manufactured by Nippon Synthetic Chemical Industry Co., Ltd. and 10 parts of the photopolymerizable monomer "Viscoat #300" manufactured by Osaka Organic Chemical Industry Co., Ltd. by 2-butanone. In a solution in which the solid content of 50 parts of the polymethyl methacrylate "MN" manufactured by Kaneka Co., Ltd. is 50%, and the total solid content concentration is 50%, the ratio is 3 parts with respect to 100 parts of the solid content. "Irgacure 819" manufactured by Nagase Industries Co., Ltd. is used as a photopolymerization initiator.

(2) Design printing ink

An ink for printing a concave plate comprising 10 parts of a black pigment, 5 parts of nitrocellulose, 15 parts of an alkyd resin, 30 parts of toluene, 30 parts of ethyl acetate, and 10 parts of isopropyl alcohol was prepared.

(3) Coating liquid for the subsequent layer

Under the condition of heating and refluxing, Polyester "SP-185" (polyester resin) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. is relative to "toluene and 2" The butanone was stirred and dissolved in such a manner that the mixed solvent of 4:1 (weight ratio) became 20%.

It is understood that the polyvinyl alcohol-based film No. 1- consisting of a composition containing 1 part by mass or more of the nonionic surfactant (B) having an oxyethylene group and an oxypropylene group, based on 100 parts by mass of the polyvinyl alcohol. a peeling strength of 4, and a polyvinyl alcohol-based film No. 5, 6 composed of a composition of a nonionic surfactant having only one of an oxyethylene group or an oxypropylene group blended with 1 part by mass or more. The peel strength is 1/10 or less, and the mold release property is excellent. In addition, even when a nonionic surfactant (B) having an oxyethylene group and an oxypropylene group was used, no decrease in peel strength was observed in No. 7 having a content of less than 1 part by mass. Therefore, it is understood that the nonionic surfactant having 1 part by mass or more of an oxyethylene group and an oxypropylene group is effective for reducing the peel strength with respect to 100 parts by mass of the polyvinyl alcohol. In addition, when the nonionic surfactant having an oxyethylene unit and an oxypropylene unit is contained in an amount of 1 part by mass or more, the blocking resistance with respect to the adhesion between the polyvinyl alcohol-based films is hardly affected.

Further, it is known that the transfer layered body has a surface glossiness as compared with the case of using the film for thermal transfer film No. 1-4 having a small peel strength and the case of using the heat transfer film No. 5-7 having a large peeling strength. Excellent writeability.

[Industrial availability]

Since the polyvinyl alcohol-based film of the present invention is excellent in mold release property, it is useful as a base film for a separator or a film for transfer.

Claims (13)

A polyvinyl alcohol-based film containing 1 to 20 parts by weight of an oxyethylene group and an oxypropylene group-containing nonionic surfactant with respect to 100 parts by weight of the unmodified polyvinyl alcohol resin (A). (B), the nonionic surfactant (B) is a fatty acid ester selected from the group consisting of an alkyl ether (B1) to which an aerobic vinyl group and an oxypropylene group are added, and an aerobic vinyl group and an oxypropylene group are added. (B2) and at least one of the group consisting of the polyol ether (B3) to which an aerobic vinyl group and an oxypropylene group are added, and the total number of structural units of the oxyethylene group and the number of structural units of the oxypropylene group is 20 ~100. The polyvinyl alcohol-based film of claim 1, wherein the number of structural units of the oxyethylene group in the nonionic surfactant (B) is from 1 to 70, and the number of structural units of the oxypropylene group is from 1 to 70. . The polyvinyl alcohol-based film of the first aspect of the invention, wherein the ratio of the oxyethylene group to the oxypropylene group in the nonionic surfactant (B) (oxyethylene/oxypropylene group) (mole ratio) ) is 10/90~90/10. The polyvinyl alcohol-based film of the first aspect of the patent application, wherein the non-ionic surfactant (B) has an HLB of 2 to 18. The polyvinyl alcohol-based film according to any one of claims 1 to 4, wherein the polyoxyethylene block is used as a hydrophilic portion and the polyoxypropylene block is used as a hydrophobic portion. The polyvinyl alcohol-based film according to any one of claims 1 to 4, wherein the unmodified polyvinyl alcohol-based resin (A) has a degree of saponification of 70 mol% or more. The polyvinyl alcohol-based film according to any one of claims 1 to 4, wherein the unmodified polyvinyl alcohol-based resin (A) has a viscosity of 5 to 70 mPa at 4 ° C in an aqueous solution of 20 ° C. s. A polyvinyl alcohol-based film containing 1 to 20 parts by weight of an oxyethylene group and an oxypropylene group-containing nonionic surfactant with respect to 100 parts by weight of the unmodified polyvinyl alcohol resin (A). (B), the nonionic surfactant (B) is a fatty acid ester selected from the group consisting of an alkyl ether (B1) to which an aerobic vinyl group and an oxypropylene group are added, and an aerobic vinyl group and an oxypropylene group are added. (B2) and at least one of the group consisting of the polyol ether (B3) to which an aerobic vinyl group and an oxypropylene group are added, and the total number of structural units of the oxyethylene group and the number of structural units of the oxypropylene group is 20 ~100, the number of structural units of the oxyethylene group in the nonionic surfactant (B) is 1 to 70, the number of structural units of the oxypropylene group is 1 to 70, and the ratio of the oxyethylene group to the oxypropylene group is (Oxyethylene/oxypropylene) (Mohr ratio) is from 10/90 to 90/10. The polyvinyl alcohol-based film according to claim 8, wherein the hydrophilic portion of the nonionic surfactant (B) is a polyoxyethylene block, and the hydrophobic portion is a polyoxypropylene block, and the HLB is 2 to 18. A method for producing a polyvinyl alcohol-based film obtained by casting a polyvinyl alcohol-based resin aqueous solution in an amount of 100% by weight based on the unmodified polyvinyl alcohol-based resin (A). a portion containing 1 to 20 parts by weight of a nonionic surfactant (B) containing an oxyethylene group and an oxypropylene group, The nonionic surfactant (B) is selected from the group consisting of an alkyl ether (B1) obtained by addition of an oxyethylene group and an oxypropylene group, a fatty acid ester (B2) having an addition of an oxyethylene group and an oxypropylene group, and an addition. At least one of the group consisting of an aerobic vinyl group and an oxypropylene group polyol ether (B3), and the total number of structural units of the oxyethylene group and the number of structural units of the oxypropylene group is 20 to 100. The polyvinyl alcohol-based film of claim 10, wherein the polyvinyl alcohol-based resin aqueous solution has a concentration of 10 to 30% by weight. A layered substrate for transfer, which is provided with a base film [I], a curable resin layer [II], a printed layer [III] composed of a polyvinyl alcohol film according to any one of claims 1 to 9 ]. The layered product for transfer of the base film [I] has a surface roughness (Ra) of 1 μm or less on the side of the curable resin layer [II] of the base film [I].